Natural Resources Of Bulgaria

Coal, petroleum, and natural gas are some of the natural resources of Bulgaria.

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Bulgaria is a European nation that spans an area of roughly 42,855 square miles and it is one of the top 100 economies globally. In 2017, the Bulgarian gross domestic product was ranked 74th in the world while its per capita gross domestic product was the 63rd highest in the world. The Bulgarian economy is classified as an open economy with the private sector playing a huge role in the country's economic success. Bulgaria's economy has undergone intensive reformation since the 1940s when the country was mainly dependent on agriculture. To reduce the reliance on arable land, the Bulgarian government focused on the development and exploitation of other natural resources such as forests, minerals, and fish.

Bulgaria has been blessed with a variety of mineral resources, ranging from iron ore to copper, that was mainly developed during the communist era. After the period ended, the mining industry in Bulgaria began to lose in significance which led to several significant deposits being left unexploited. The decline of Bulgaria's mineral sector has been attributed to several factors primarily the lack of sufficient capital to purchase modern machinery. The Bulgarian government estimated that during the early 21st century, the mining industry only contributed 2% to the country's gross domestic product each year.

One of Bulgaria's most essential minerals is coal. It has vast deposits of the mineral mainly situated in its western region. Geological data indicated that most of the coal in Bulgaria is lignite, a coal variety with lower heat content than other coal varieties. The Bulgarian government estimates that the nation has close to 4.5 billion tons of lignite most of which, close to 70% according to some estimates, is situated in the Maritsa Iztok Coal Basin. The rest of Bulgaria's lignite is situated within the Lom coalfield and the Sofia Coal Basin. Apart from lignite, Bulgaria also has significant deposits of anthracite, the most valuable coal variety due to its high heat output, which is estimated to be around 1.2 billion tons. Bulgaria is unable to exploit its vast anthracite resources because they are located in extremely inaccessible areas. Bulgaria also has roughly 800 million tons of brown coal spread out all over the country in regions such as Bobov Dol and Pernik.

Water is one of Bulgaria's most important natural resources since it is used in energy generation. Some of the Bulgarian rivers used for hydropower generation include the Krka River, the Arda River, and the Vacha River. In 2010, according to statistics from the Bulgarian government, hydroelectricity accounted for close to 10% of the electricity used in Bulgaria. Fifteen hydroelectric power stations, all operated by a state agency, provided close to 95% of all the hydropower used in Bulgaria.

The Bulgarian people also consider wind to be one of their most important natural resources. Several experts from the European Union believed that Bulgaria has great potential to be a leading producer of wind energy. Bulgaria's wind energy sector experienced significant growth from 2004 to 2012, but since that time it has stagnated.

Natural Gas

According to geological surveys, Bulgaria is believed to have 17 trillion cubic feet of natural gas. It is thought that Bulgaria's reserves could satisfy the country's demand for natural gas for almost 100 years. There are several major fields of natural gas in Bulgaria such as the Chaika, Izgrev and Deventsi gas fields. The Chaika field is one of the country's youngest offshore gas fields as PetroCeltic discovered it in 2013. The Chaika field is believed to contain nearly 0.55 cubic miles of natural gas. PetroCeltic also discovered the Izgrev offshore field in 1993. The Izgrev field has been proven to have 1.89 cubic miles of natural gas.

Apart from natural gas, Bulgaria also has vast deposits of oil with some estimates indicating that the nation could have 200 million barrels of oil. The Bulgarian government, seeking to replicate the success of several neighboring states, invited several countries to explore oil within its territorial waters and in 2016, the company Total discovered deposits of oil within the Black Sea. To properly explore the oil field, the company planned to drill two wells. In 2018, another company discovered oil while drilling within the Bulgarian section of the Black Sea.

The World Bank estimated that forests covered roughly 35.22% of Bulgaria's total land area in 2015. Since 2004, when the nation's forest cover was approximately 33%, the amount of forested land in Bulgaria has been increasing gradually. The increase in the forested area was due to a concerted effort by the Bulgarian people to raise the country's forest cover. The Bulgarian forests are of great ecological significance since they provide habitats to more than 500 unique animal species. Roughly 5% of the animals that live in Bulgaria are considered threatened.

Arable Land

From 2004 to 2010, the amount of land devoted to agriculture in Bulgaria declined gradually, but from 2010 to 2012 the amount of agricultural land has increased. The Bulgarian government estimated that in 2016, the agricultural sector contributed 5% of the country's gross domestic product. The Bulgarian labor department estimated that approximately 7% of the country's population was employed in the agriculture sector.

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Project Description

Forests have played a crucial role in the development of human culture. The word forest, deriving from the old Latin word ‘foris’, literally means ‘outside’, or outside of human civilization. It is this exteriority that has made the forest a particularly fertile ground for our myths and our stories to grow and evolve. Not only have forests provided raw materials for our constructions, they have also contributed to the development of our culture: “From the family tree to the tree of knowledge, from the tree of life to the tree of memory, forests have provided an indispensable resource of symbolization in the cultural evolution of humankind” (Harrison, 8). Yet despite this deep cultural connection, we continue to have an unbalanced, parasitic like relationship with nature, where we treat trees and natural elements simply as raw material in support of our infrastructure, lives, and cultural development.

A subtle shift in perspective has taken place in recent years, that suggests a renewed recognition of the liveliness of trees and of our obligation to protect the rights of the forest. Scientific discoveries have proven that trees are living beings, are highly social, have families, can learn, and can even communicate with each other (Wohlleben, 7). In New Zealand in 2014, the Te Urewera Act was passed, granting legal personhood to the national park of the same name. In the same country in 2017, parliament passed the Te Awa Tupus (Whanaganui River Claims Settlement) Bill, which conferred a legal personality to the Whanganui River. This bill guaranteed the river’s ‘personhood’ and along with it the same rights and responsibilities as a person. The government did this as a solution to a land dispute with local indigenous peoples, but in offering this formal recognition of life it also provides a strong rationale for changing our relationship with natural resources on this planet, and to reconsider how we consume them. If we begin to ‘see’ and ‘understand’ the sentience of the ecosystem of a forest, perhaps then we might begin to realise the necessity of protecting them as valuable individuals.

Foresta Inclusive is a technologically (Internet) connected indoor and outdoor art installation that links the ecosystem of a forest through a sculptural sensor hub, to an art installation within a gallery. This project proposes to make perceptible to the human senses, the slow and subtle movements of trees and surrounding ecology, in order to find ways to create a context for in-gallery human/forest interaction and collaboration. This work is not meant to replace real life experiences within a forest, but rather to materialize the often-invisible life movements of the forest and to use technology as a tool to give voice to nature within a human cultural space. Foresta Inclusive is a work-in-progress and therefore includes the continued development of three main conceptual/practical components:

Physical connection to the forest: During the Ayatana residency entitled ‘Germinate’, which involved connecting artists with scientists and other plant specialists in Gatineau (QC) in June 2019, I identified the visual metaphor I wanted to work with for this project. I am interested in shifting the relationship between human/technology/culture and the ecosystem of the forest, from a parasitic type relationship, to one that is mutualistic or commensalistic. A mutualistic relationship is where both parties benefit from the interaction, such as protozoa in the stomach of a termite, which digests the consumed wood in the termite’s stomach, allowing them to get nutrients and sustenance and in turn the termite offers a safe place for the protozoa to live. A commensalistic relationship is where one-party benefits, and the other is not affected, such as orchids that grow on trees. It is clear that human/culture/technology needs nature, but what does nature need from us? Perhaps it needs us to recognize its ‘aliveness’, and therefore embrace the ethical implications that comes from that recognition.

Historical/Contemporary Data Collection: For this project I will collect live data from a forest and also historic climate data from the same geographic location using dendrochronological studies. Dendrochronology is the scientific method of dating tree rings by using core samples taken from live trees or wooden constructions made from old timber. Data collected using this method can also provide historic information about the climate and atmosphere, so for example we can learn if there was a drought in 1652. As a co-investigator in a Social Sciences and Humanities Research Council Partnership Grant ‘Environments of Change’, based at the University of Waterloo, I have access to the forest at Herstmonceux Castle in East Sussex, UK and also the scientists, climatologists and historians affiliated with the project. While this forest is relatively young, I will have access to historical climate data dating back to medieval times given the age of the wooden structures of the area. For collecting the live data, I am developing a solar powered sculptural sensor hub, comprised of a number of sensors (temperature, particulate, humidity) and a GSM enabled microcontroller that connects to the Internet remotely. This system will send real-time data to the Internet of Things platform Shiftr.io, which is essentially an enabling protocol that lives on-line, linking the connected sensors with the user application, in this case the artwork in gallery.

Materialization of collected data: On the gallery side, I will materialize this data in the form of an installation comprised of light, sound, projection and objects. This part of the project is unmaterialized as of yet, except for a number of small prototypes. I will use the historic/live data to create an atmosphere within a gallery, but also create an experience, where the movement of the viewer body can explore the historic and lived realities of the ecosystem of the Herstmonceux forest.


Chendebji Chorten

Situated between Trongsa and Bumthang, the uniquely beautiful Chendebji Chorten is a welcome sight as you near the heart of central Bhutan. Built in the style of Boudhanath Stupa of Nepal, this spectacular stupa is set up perfectly against the lush green surroundings and appears to ceremoniously observe everything in its vicinity.

It was built in the 18th Century by Lama Zhida to suppress the remains of an evil spirit known as Ngyala Dhuem, a renowned Bhutanese folklore figure. Locals still talk of the chill that runs down their spine every time they are near this Chorten, a testimony to the rich culture of storytelling that still exists in Bhutan.

Chendebji Chorten is believed to stand on the meeting point of three ridges with that of the three edges of the sky. It is a popular lunch spot for tourists and locals with a restaurant situated a few meters away.


С Новым 2016 годом!

My Dear Students!

As 2015 comes to an end, I wanted to take this time to reflect on the year and look forward to what lies ahead.

First and foremost I would like to thank you all for your hard work, dedication and results. You are all great. The passion and heart you bring to work daily truly makes a difference. I am confident in saying that you have gained a lot in 2015; not only the knowledge but also plenty of memorable experiences.

I am proud to have provided new information, interesting classes and satisfaction. Thank you for allowing me to continue doing what I love – making dreams come true! If I can continue to do this, these is nothing else I require. Looking forward to seeing you all in 2016!

May 2016 bring all good health, joy and peace.

Happy New Year!


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Hi, we have reports that produce model graphics in excel spreadsheets. The problem we find is that some models are not clear therefore we cannot read the contents or share with users.  In some cases, we are able to right-click on an image in excel and then edit the picture to change it to emf format. This resolves the issue in some cases but affects other formatting elements.

We've changed the formats from xls to xlsx and that doesn't resolve the problem. Our code also tries to use twips to determine the size of the image in terms of row and column counts and I'm unsure if that is the cause of the blurriness.

I've also asked our Software AG representative to log an Empower call for assistance but I thought that someone here may have resolved this issue already.

Any assistance would be appreciated?


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University of Wisconsin: Simulating complex catalysts key to making cheap, powerful fuel cells

“Understanding reaction mechanisms is the first step toward eventually replacing expensive platinum in fuel cells with a cheaper material,” says Manos Mavrikakis, a UW-Madison professor of chemical and biological engineering.
Mavrikakis and colleagues at Osaka University in Japan published details of the advance Monday, Aug. 8, in the journal Proceedings of the National Academy of Sciences (“Ab initio molecular dynamics of solvation effects on reactivity at electrified interfaces”).

Methanol Molecules
Modeling how methanol interacts with platinum catalysts inside fuel cells in realistic environments becomes even more complicated because distances between the atoms can change as molecules dance near the charged surface. (Image: Manos Mavrikakis)

Fuel cells generate electricity by combining electrons and protons — provided by a chemical fuel such as methanol — with oxygen from the air. To make the reaction that generates protons faster, fuel cells typically contain catalysts. With the right catalyst and enough fuel and air, fuel cells could provide power very efficiently.

Someday, fuel cells could make laptop batteries obsolete. Mere tablespoons of methanol could potentially provide up to 20 hours of continuous power. But alternatives to the expensive platinum catalyst in today’s fuel cells haven’t emerged because scientists still don’t fully understand the complicated chemistry required to produce protons and electrons from fuels.

And finding a good catalyst is no trivial task.

“People arrived at using platinum for a catalyst largely by trial and error, without understanding how the reaction takes place,” says Mavrikakis. “Our efforts developed a big picture of how the reaction is happening, and we hope to do the same analysis with other materials to help find a cheaper alternative.”

At first glance, the chemistry sounds straightforward: Methanol molecules awash in a watery milieu settle down on a platinum surface and give up one of their four hydrogen atoms. The movement of those electrons from that hydrogen atom make an electric current.

In reality, the situation is not so simple.

“All of these molecules, the water and the methanol, are actually dancing around the surface of the catalyst and fluctuating continuously,” says Mavrikakis. “Following the dynamics of these fluctuating motions all the time, and in the presence of an externally applied electric potential, is really very complicated.”

The water molecules are not wallflowers, sitting on the sidelines of the methanol molecules reacting with platinum; rather, they occasionally cut in to the chemical dance. And varying voltage on the electrified surface of the platinum catalyst tangles the reaction’s tempo even further.

Previously, chemists only simulated simplified scenarios — fuel cells without any water in the mix, or catalytic surfaces that didn’t crackle with electricity. Unsurprisingly, conclusions based on such oversimplifications failed to fully capture the enormous complexity of real-world reactions.

Mavrikakis and colleagues combined their expertise in two powerful computational techniques to create a more accurate description of a very complex real environment.
They first used density functional theory to solve for quantum mechanical forces and energies between individual atoms, then built a scheme upon those results using molecular dynamics methods to simulate large ensembles of water and methanol molecules interacting among themselves and with the platinum surface.
The detailed simulations revealed that the presence of water in a fuel cell plays a huge role in dictating which hydrogen atom breaks free from methanol first — a result that simpler methods could never have captured. Electric charge also determined the order in which methanol breaks down, surprisingly switching the preferred first step at the positive electrode.

This type of information enables scientists to predict which byproducts might accumulate in a reaction mixture, and select better ingredients for future fuel cells.
“Modeling enables you to come up with an informed materials design,” says Mavrikakis, whose work was supported by the Department of Energy and the National Science Foundation. “We plan to investigate alternative fuels, and a range of promising and cheaper catalytic materials.”

The results represent the culmination of six years of effort across two continents. Jeffrey Herron, the first author on the paper, started developing the methodologies during a summer visit to work under the paper’s second author, Professor Yoshitada Morikawa in the Division of Precision Science & Technology and Applied Physics at Osaka University.
Herron, who completed his doctorate in 2015 and is now a senior engineer for The Dow Chemical Company, further refined these approaches under Mavrikakis’ guidance over several subsequent years in Madison.
“A lot of work over many years went into this paper,” says Mavrikakis. “The world needs fuel cells, but without understanding how the reaction takes place, there is no rational way to improve.”
Source: University of Wisconsin-Madison

Read more: Simulating complex catalysts key to making cheap, powerful fuel cells

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Molecular Dynanmics: Visualizing the Invisible

Palladium Nano id36700

He knows what the atoms in his starting nanoparticles look like. He knows their motion follows the laws of Newtonian physics. His colleagues have seen what the resulting particles look like after collision experiments. Once his simulation is complete, Grammatikopoulos compares his end products with his colleagues to check his accuracy. Grammatikopoulos most recently simulated how palladium nanoparticles interact, published in Scientific Reports on July 22, 2014 (“Coalescence-induced crystallisation wave in Pd nanoparticles”).

simulation of palladium nanoparticles colliding at different temperatures

Grammatikopoulos simulated two palladium nanoparticles colliding at different temperatures. The hotter the temperature, the more homogenous the resulting product, and the further the atoms in the particle crystallize. (click on image to enlarge)

Palladium Crystallization at 300K. Grammatikopoulos created this simulation of palladium nanoparticles colliding at 300 Kevin, or about 27 degrees Celsius. The nanoparticles meet, then fuse, then crystallize in orderly planes.

Palladium Crystallization at 1000K. Grammatikopoulos created this simulation of palladium nanoparticles colliding at 1000 Kevin, or about 727 degrees Celsius. At this hot temperature, the nanoparticles meet, fuse, and crystallize, forming one large homogenous product.

Source: By Poncie Rutsch, Okinawa Institute of Science and Technology


A comment on the key concepts of the theory of ayer

Introduction One of the major claims made regarding qualitative methods is that they diverge from scientific explanation models in terms of the need for hypothesis testing. A scientific hypothesis is based on a background theory, typically assuming the form of a proposition whose validity depends on empirical confirmation. Otherwise, a hypothesis is nothing but an imaginative conjecture.

A comment on the key concepts of the theory of ayer

Contact Author There were philosophers before Plato but they mostly served as tutors for children of the rich. Plato was the first to ask many of the questions that philosophers would be obsessed with for the next couple thousand years. Plato and Socrates It is difficult to talk about Plato without talking about Socrates and it is difficult to talk about Socrates without talking about Plato.

Socrates never wrote anything down and so a lot of our perception of who he was and what he thought comes from Plato. What we know of Socrates is mostly as a literary character. The legend about Socrates goes that the Oracle of Delphi proclaimed him the wisest man in all of Athens.

Confused by this, Socrates went around and talked to all the men who he thought were wiser than he was. After talking to them and questioning them he found that their beliefs were full of contradictions and when he pointed this out to them they became upset.

Afterwards, he came away with the belief that the oracle had been right. Socrates established the role of the philosopher to question everything. Because he constantly questioned the values of society, criticized politicians and proposed ideas that made the establishment nervous he was finally put on trial for corrupting the youth and for not worshipping the correct Gods.

With The Republic, Plato struck out on his own philosophical territory, and while it still has a literary structure with Socrates as our hero, we are seeing a systematic philosophy start to take hold for the first time. Early in the book Socrates encounters the character of Thrasymachus who insists that justice is the interest of the stronger.

This was a common viewpoint in ancient Greece.

Key Concepts of John Rawls' Philosophy | Owlcation

This was a society that valued strength above everything else and it was Thrasymachus who held the view that it was acceptable to dominate others, lie, cheat and steal if one of strong enough to get away with it.

A story we are given to illustrate this is the ring of Gyges. Gyges is given a ring that makes him invisible and the story is used to argue that no man would be just if he could commit unjust acts without being caught or punished.

What Virtue Ethics states is that the reasoning of what is moral is determined by the person moral agent rather than by rules or consequences. These parts are reason, spirit and appetite. He argues that the human soul must have at least two parts in order to explain why we have so many psychological conflicts.

It could be seen that reason is our thinking ability to judge, spirit our emotional ability to feel empathy and appetite our desires but you will always have people who read the book and see it differently.

The point for Plato however, is that we need to balance these three parts of our souls in order to make good ethical choices. The whole point of being moral is to balance these three parts of us to keep us healthy and sane. Letting one take too much control of our minds is not good for us and leads to bad decisions.

His defenders point out that while it may seem that way to us today we must look at it in historical context. Plato was thinking of his ideal government as a city state and this is a relatively small area where those who did not approve of the government could move to another city state that they found less objectionable.

Private families no longer exist and the social mobility of women is greatly increased because they are no longer expected to simply play the role of wife and mother.Books, Essays, Quotes, Interviews on W.

V. Quine, mathematician and philosopher including list of books, articles, dissertations, essays, students, and travels.

Includes links to other Willard Van Orman Quine Internet resources as well as to other Family Web Sites by Douglas Boynton Quine. J. L. Mackie - Ethics~ Inventing Right and Wrong (, ) - Free ebook download as PDF File .pdf), Text File .txt) or read book online for free.

tabula rasa) and behavior is shaped through positive reinforcement or negative reinforcement [2].

A comment on the key concepts of the theory of ayer

Oct 07,  · Rawls is considered by many to be the most important political philosopher of the 20th Century and his landmark book, A Theory of Justice, is praised for having attempted to unite a lot of competing political theories that many had judged incompatible.

In the 19th century, political philosophy had split between the radical egalitarianism of Karl Marx and the concepts of personal liberty and Reviews: 5. This is a review of the concepts and common debates within ‘Theory of Change’ (ToC) material, resulting from a search and detailed analysis of available donor, agency and expert guidance documents.

pfmlures.com: An Introduction to the Philosophy of Science (): Rudolf Carnap: Books.

Constructivism - Learning Theories


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Reduced Graphene Oxide/Carbon Nanotube Composites as Electrochemical Energy Storage Electrode Applications

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We demonstrate an electrochemical reduction method to reduce graphene oxide (GO) to electrochemically reduced graphene oxide (ERGO) with the assistance of carbon nanotubes (CNTs). The faster and more efficient reduction of GO can be achieved after proper addition of CNTs into GO during the reduction process. This nanotube/nanosheet composite was deposited on electrode as active material for electrochemical energy storage applications. It has been found that the specific capacitance of the composite film was strongly affected by the mass ratio of GO/CNTs and the scanning ratio of cyclic voltammetry. The obtained ERGO/CNT composite electrode exhibited a 279.4 F/g-specific capacitance and showed good cycle rate performance with the evidence that the specific capacitance maintained above 90% after 6000 cycles. The synergistic effect between ERGO and CNTs as well as crossing over of CNTs into ERGO is attributed to the high electrochemical performance of composite electrode.

In the last decades, supercapacitors have been widely studied in order to meet the rapidly growing demands of new energy-device with high-power, high energy, high charge/discharge rates and long cyclic life [1]. Generally, activated carbon, carbon nanotubes, mesoporous carbon, nano-carbon have been investigated for use as electrodes in electrochemical double-layer supercapacitors. Besides, the pseudo-supercapacitors materials, conductive polymers and transition metal oxides, storing energy through a faradic process have been widely explored [2, 3]. Recently, graphene and its composites have attracted a wide range of research for the electrode material because of their large surface area, high carrier mobility, and excellent electrochemical stability [4,5,6]. As a one-atom thick layer of carbon atoms arranged in a honey-comb lattice, graphene is well-known for its high specific capacitance as energy storage applications [7, 8]. However, large area preparation of high quality graphene films as energy storage applications are still in challenges [9, 10].

As for preparation methods, mechanical exfoliation by sonication [11, 12], epitaxial growth on metal or silicon carbide [13, 14], chemical vapour deposition [15,16,17], and etc have been investigated extensively. Among these methods, the electrochemical reduction of graphene oxide (GO) has aroused great research interest in recent years due to its advantages, such as relatively simple, economic, manageable and eco-friendly [18,19,20,21,22]. However, the obtained pristine electrochemically reduced graphene oxide (ERGO) exhibits low specific capacitance result from their characteristic of easy agglomerate.

Presentation of the hypothesis

Herein, some tentative works have been demonstrated to prepare highly opened reduced graphene oxide (RGO) structure incorporated with other nanostructures, such as nanoparticles [23, 24], nanotubes [25] and nanowires [26, 27]. The well interaction between the components would result in good synergistic effect in these nanocomposites, which leads to excellent electrical and electrochemical performance. However, well dispersion of these nanostructures into RGO is still challenged due to the feasible preparing method and bad interaction between various components.

Testing the hypothesis

Here, we demonstrate an in situ electrochemical method to prepare high performance ERGO composites. The high conductive carbon nanotubes (CNTs) was added into GO sheets during the reduction process of GO.

Implications of the hypothesis

Due to the entangled framework of CNTs, it could be beneficial to reduce agglomerate of the GO sheets and the obtained ERGO shows more highly opened structures. Moreover, the excellent conductivity of CNTs would also beneficial to reduce the GO into ERGO with fast speed and more efficiently. With finely controlling of addition ratio, the obtained ERGO/CNTs nanocomposites show excellent electrical and electrochemical performance, which shows promising future as electrochemical energy storage electrodes.

Synthesis of ERGO/CNTs

The GO was prepared from natural graphite flakes by modified Hummer’s method. An aqueous GO dispersion solution about 1.5 mg/ml was used to prepare composites, and the size of the GO sheet is controlled with less than 650 nm. The graphite flakes (XF055 7782-42-5) and a water solution of CNT (XFWDST01 1333-86-4) dispersion were also purchased from Nanjing XFNANO Materials Tech., Co., Ltd. All materials were used as received.

For the preparation of composite GO/CNT solution, the GO solution was firstly ultrasonicated in an electric-heated thermostatic water bath for 20 min at 40 °C. Then, CNT solution purchased from XFNANO was added into GO solution with the different mass ratios and continued to stir for 15 min. Subsequently, a spray-coating method was used to deposit GO and CNTs onto ITO substrate, and then, the substrate was treated in a vacuum oven at 60 °C for 2 h. Finally, the obtained GO/CNT films were put into an electrolytic tank, the GO was electrochemically reduced into ERGO, and an ERGO/CNT composite film was obtained. Electrochemical reduction of as-prepared GO/CNT films were carried out in a three-electrode system (CHI660D electro-chemical workstation, Chenhua, Shanghai, China) with a 0.5 M (pH 6.0) Na2SO4 aqueous solution as working electrolyte. A platinum disk and an Ag/AgCl electrode were used as the counter and reference electrode, respectively.

The electrical conductivity of ERGO and ERGO/CNTs was characterized by a four-probe testing system with a SZ-100 model (Baishen, Suzhou, China). FT-IR spectrum was characterized with an ALPHA analysis instrument (Germany). Surface morphologies of ERGO and the composite films were characterized by scanning electron microscopy (SEM) with a model Philips XL30-FEG. X-ray diffraction system (XRD, X’Pert Pro MPD DY129) and Raman spectroscopy (Advantage 633 nm) were used to investigate the crystallographic structure of the films. The cyclic voltammetry (CV) and galvanostatic charge/discharge curves (GCD) of composite films were also obtained from CHI660D electro-chemical workstation (Chenhua, Shanghai, China).

Results and Discussion

The purpose about addition of CNTs into GO sheets is that the CNTs cannot only supply the entangled structure after the physical mixing to avoid the agglomerating of GO sheets but also improve the conductivity of composite GO/CNT films for fast reduction of GO into ERGO. Figure 1 shows the SEM images of ERGO and ERGO/CNT films electrochemically reduced from GO/CNT films with a different GO/CNT mass ratio. The obvious color change of composite films from faint yellow to deep black (as shown in the inset of Fig. 1b) indicates the successful reduction of GO into ERGO. From Fig. 1a, b we can see the entangled structure of CNTs and the ridge-like wrinkle structure of ERGO are exhibited in composite films. The CNTs have embedded in ERGO evenly after the physical mixing and electrochemical reduction. The embedded CNTs can protect the ERGO sheets from agglomerating effectively, and this wrinkled and entangled structure is able to offer higher surface area than pristine ERGO. This highly opened composite nanostructure is suitable for easily and sufficiently adsorbing electrolyte ions onto electrode surface during electric double-layer energy storage. Furthermore, with the increasing mass ratio of CNTs (as shown in Fig. 1c, d), more CNTs penetrate into ERGO as a support and an aggregated structure of CNTs are presented.

Fig. 1

SEM images of ERGO (a) and ERGO/CNTs obtained from GO/CNTs with different mass ratios: b GO/CNTs = 100:1, c GO/CNTs = 50:1, and d GO/CNTs = 10:1; the inset images in (b) are photo pictures of GO/CNTs before and after electrochemical reduction

The functional groups of GO and ERGO are characterized by FT-IR spectrum, which are shown in Fig. 2. As for graphene oxide, the peak at 3424 cm−1 is ascribed to O–H stretch. The peaks at 1735 and 1629 cm−1 are a result from C=O stretch and aromatic C=C, respectively. The peak at 1222 cm−1 rises from O–H bending and the peak at 1052 cm−1 are ascribed to epoxy C–O stretch and alkoxy C–O stretch. These identified function groups by FT-IR spectrum indicates the oxygen-containing nature of GO. After an electrochemical reduction, the obviously weakened peaks in spectrum are 1735 and 1222 cm−1 [28], indicating the well elimination of these oxygen-containing groups.

Fig. 2

FT-IR spectrum of GO and ERGO

The reduction process of GO is also confirmed by the change of conductivity of nanocomposites, as shown in Table 1. It can be seen that, firstly, the addition of CNTs into GO sheet has improved the electrical ability of GO/CNTs composites. With the addition ratio of GO to CNTs from 0 to 50:1 and 10:1, the electrical resistance of nanocomposite varies from a MΩ/sq. to a kΩ/sq. level. After the electrochemical reduction, an obvious enhancement of electrical conductivity is achieved in nanocomposite, indicating effectively reducing of GO into ERGO. The remarkable improvement in electrical conductivity of ERGO film is attributed to the elimination of the oxygen functionalities during the electrochemical reduction, and the symmetrical sp2 C=C bonds are rebuild for better transferring of carriers [20]. Accordingly, with the increasing of electrical conductivity, a more continuous and complete conducting path is formed in ERGO/CNT composite. The results in Table 1 also reveal that, after the electrochemical reduction, there is no distinct conductivity difference found between the ERGO and ERGO/CNTs nanocomposite, and this results indicate that the reduced ERGO exhibits a comparable electrical conducting ability with CNTs.

Table 1 Electrical conductivity of GO and GO/CNTs with different mass ratios before and after electrochemical reduction

The structure change of GO after the electrochemical reduction is characterized by Raman spectra and X-ray diffraction analysis, which are shown in Fig. 3. From Fig. 3a, a D band at ~ 1345 cm−1 and a G band at 1583 cm−1, which are assigned to the disordered structural defects and the E2g phonon of sp2 carbon atoms [29], are presented, respectively. It is noted that the ERGO film exhibits a higher ID/IG ratio than the pristine GO film due to the decreased amount of defects after electrochemical reduction. The ERGO/CNT composite shows a lower ID/IG ratio than ERGO due to the addition of CNTs.

Fig. 3

a Raman spectra and b X-ray diffraction spectra of the pristine GO, ERGO, and ERGO/CNTs

XRD patterns of GO, ERGO, and ERGO/CNTs also reveal the electrochemical reduction of GO into ERGO after the mixing with CNTs (as shown in Fig. 3b). As for GO, an additional peak at 10.3° is observed, which is attributed to the (001) diffraction peak of GO. The larger interlayer distance of GO nanosheets might be due to the existence of oxygen-containing functional groups on the sheet surface [30]. After the electrochemical reduction, the (001) diffraction peak of GO disappears and a broad diffraction peak (002) approximately 24.3° appears. The interlayer spacing of ERGO was 0.39 nm, slightly larger than that of graphite, which was resulted from the small amount of residual oxygen-containing functional groups or other structural defects. Besides the feeble and broad diffraction peak (002), the ERGO/CNTs also show a weak diffraction peak at 8.4°. We conclude that comes from the mixing of GO with CNTs, and this mixing structure leads to the shift of diffraction peak after electrochemical reduction of GO.

The electrochemical reduction process of GO and GO/CNTs are characterized by CV curves (as shown in Fig. 4). Both GO film and the GO/CNTs film are electrochemically reduced at the potential range from 0 to − 1.4 V in a 0.5 M Na2SO4 electrolyte solution (pH 6.0). Obviously, the cathodic peak appeared at about − 0.75 V during the first cycle results from the partial elimination of the major functional groups on the surface of GO sheets, such as epoxy, carboxyl, and hydroxyl [20]. It should be noted that, compared with the pristine GO film, the reduction process of the composite GO/CNT films is more rapid with the evidence that the GO/CNT film shows larger reaction current at the first cycle. Moreover, the GO/CNT films come to stable current with less reaction cycles, which means that the reducing process of GO in GO/CNTs is faster than that of pure GO at the same electrochemical conditions. We conclude that the high conductivity of CNTs improves the electrical ability of GO/CNTs, and the enhanced conductivity results in faster electron transferring between the electrode and GO/CNTs, leading to a faster reduction process of GO into ERGO.

Fig. 4

Electrochemical reduction of a GO and b GO/CNTs (mass ratio 50:1) in 0.5 M Na2SO4 (pH 6.0) at a scan rate of 50 mV/s

Figure 5 shows cycle voltammetry curves of ERGO and ERGO/CNTs electrochemically reduced from GO/CNTs with different mass ratios at 50 mV/s. All the films were prepared by CV method at a scan rate of 50 mV/s. The results reveal that the mixing ratio of GO and CNTs in composites takes a great effect on specific capacitance of composite electrodes. The incorporation of high surface-to-volume ratio CNTs improves the energy storage density of electrode greatly. Table 2 shows the calculated specific capacitance of different electrodes. From Table 2, we can see the specific capacitance of composite electrode dramatically increases from 156.3 to 279.4 F/g with the increasing of CNT/GO mass ratio, which is reasonable for the surface area increasing of composite electrode is due to the appropriate addition of CNTs and corresponding benefits of reducing agglomerate of GO sheets. The CNT-enriched composite electrode exhibits obviously larger specific capacitance than pure ERGO, and these specific capacitance results are well consistent with the result of CV testing. However, compared with the 50:1 and 10:1 mass ratios, the further increasing of CNTs does not obviously increase the specific capacitance accordingly, and a reduced specific capacitance of electrode is observed. We conclude that high mass ratio of CNTs in composite structure results in an unpredicted agglomeration of CNTs, which leads to the inadequate interaction of CNTs with ERGO sheets for further improving the efficient surface area of composite. So, controlling the distribution and loading of CNTs in ERGO matrix during the electrochemical reduction process is very important to optimize composite electrode with high specific capacitance.

Fig. 5

Cycle voltammetry curves of ERGO and ERGO/CNTs with a different GO/CNTs mass ratio at 50 mV/s. (All films were prepared by CV at a scan rate of 50 mV/s)

Table 2 Calculated specific capacitance of different electrodes (F/g)

It is well known that high-rate capability is a key index for electrochemical capacitor electrodes. Rate performance of ERGO/CNT composite electrodes is shown in Fig. 6a. The specific capacitance of all composite electrodes shows a decreasing tendency with the increase of current due to the fact that the accessibility of electrolyte ions to active sites of the electrode is limited at higher current density [20]. The uniform distribution of CNTs into ERGO nanosheets can effectively improve the rate capability compared with pure ERGO electrode with agglomerate structure. As shown in Fig. 6a, the ERGO/CNT electrode shows the excellent specific capacitance at a current density of 1 A/g. This means that the highly opened composite electrode can not only afford high specific capacitance but also keep high capacitance retention at high current density. The uniform distribution of CNTs into ERGO sheets is reasonable for the high rate performance of composite electrodes. The CV curves of ERGO/CNT films (Fig. 6b) exhibit almost the rectangular-like shape with increasing scanning voltage, indicating a remarkable capacitive behavior and excellent reversibility of their charge/discharge process.

Fig. 6

Galvanostatic charge/discharge curves (a) and CV pattern (b) of the as-prepared film in 0.5 M Na2SO4 (pH 6.0) (mass ratio of 50:1 and scan rate of 50 mV/s)

Figure 7 is Nyquist plots of different composite electrodes. It can be seen that the composite electrodes show almost the same inner resistant (Rs) with pure ERGO electrode, which is lower than GO electrode. The composite electrode loading on CNTs shows no obvious influence on electrode Rs, indicating the comparable conductive performance of ERGO and CNTs. However, an obvious decrease of specific capacitance is observed with the increasing of GO/CNT mass ratio to 10:1, as shown in Fig. 5 and Table 2. Consequently, the excellent resistance and specific capacitance performance of composite electrode is reasonable and depending on the optimized loading and distribution of CNTs in ERGO sheets.

Fig. 7

Nyquist plots of different composite electrodes

Cycle rate performance of electrode films is also a vital factor for the practical application in electrochemical capacitor. As shown in Fig. 8, the rate performance of ERGO/CNTs (obtained from GO/CNT mass ratio = 50:1) and pure ERGO is evaluated by charging/discharging at the same current densities. For ERGO/CNT electrode, the specific capacitance maintained above 90% after 6000 cycles at a 1.2 A/g scan current density. The results indicate a good cycling ability of this nanotube/nanosheet composite electrode. The penetration of CNTs into ERGO provides a robust support for electrochemical activity of ERGO. Therefore, the alternating nanotube/nanosheet structure affords excellent mechanical strength for the long-term cycling of charge/discharge. It also can be seen in Fig. 8 that the pure ERGO electrode also presents good cycling ability only with lower specific capacitance, which results from stable EDLC and agglomerate structure of ERGO. So, it is crucial and valuable to build highly opened and stable carbon nanomaterial structure to obtain high-performance electrochemical energy storage electrode with large specific capacitance and high stability.

Fig. 8

Cycling rate performance of different electrodes at 1.2 A/g scan current density

In conclusion, we utilized a simple electrochemical method to prepare an ERGO/CNT composite films, and the pre-added CNTs into GO sheets play an important role as a reduction accelerant. High-efficiency reduction of GO was obtained, and the obtained ERGO/CNT composite film showed excellent electrochemical performance. At a mass ratio of 50:1 and the scan rate of 50 mV/s, the composite film exhibited a high specific capacitance about 279.4 F/g and showed excellent reversibility. Furthermore, this simple and versatile synthesis technique for providing graphene-based materials shows promising future in various applications such as assembly of electrochemical capacitors.

Carbon nanotubes

Cyclic voltammetry

Electrochemically reduced graphene oxide

Charge/discharge curves

Graphene oxide

X-ray diffraction system

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This work was supported by the National Science Foundation of China (51477026, 61471085, 61774030, 51707015), Chongqing Postdoctoral Science Special Foundation (Xm2017051), Scientific and Technological Research Program of Chongqing Municipal Education Commission (KJ1601111 and KJ1601122), Natural Science Foundation Project of Yongchuan (Ycstc, 2016nc2001), Open Research Foundation of Chongqing Key Laboratory of Micro/Nano Materials Engineering and Technology (KF201601), Open Research Foundation of Chongqing Engineering Research Center of New Energy Storage Devices and Applications (KF20170202), and the Scientific Research Project of Chongqing University of Arts and Sciences (R2016DQ11, P2016DQ14).

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WYY conceived of the experiment, carried out the fabrication of ERGO/CNT composites, and drafted the manuscript. YC, KT, and TJP helped to deposit the films and analyze the data. JFW helped to draft the manuscript. JHX and BCY helped to develop the idea and guided the study. All authors read and approved the final manuscript.

Correspondence to Ke Tang.

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WYY and KT are the associate professors of Chongqing University of Arts and Sciences. YC is a lecturer of Chengdu University of Information Technology. TJP is a student of University of Electronic Science and Technology of China. JFW is a professor of Chongqing University. JHX and BCY are professors of University of Electronic Science and Technology of China.

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The authors declare that they have no competing interests.

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Yang, W., Chen, Y., Wang, J. et al. Reduced Graphene Oxide/Carbon Nanotube Composites as Electrochemical Energy Storage Electrode Applications. Nanoscale Res Lett 13, 181 (2018) doi:10.1186/s11671-018-2582-6

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  • Reduced graphene oxide
  • Carbon nanotube
  • Specific capacitance
  • Nanocomposite material
  • Electrochemical reduction


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